Catalytic fluid hydroforming employing inert heat transfer solids



Oct. 18, 1955 E. w. s. NICHOLSON 2,721,157

CATALYTIC FLUID HYDROFORMING EMPLOYING INERT HEAT TRANSFER som-Ds Filed April 4, 1951 Q ooo GTS -`2 FLUE GAS T-,Ap ,io AO-v \\n W Id/ *'47 QE AC1-QQ.- rZ5 QEGEQEQATQ@ h u 4- Il ---l---ff9 -M i----l4 l |.l 4 '22 A5 5w 1g '25 -TQiDDEQ 3 I l ,49 @1: 12 was@ f icp- 42 FEED sTE/M STEAM or; 34- 33 '24 mara-r @As (mcxso 52 ELUTQIATMG r\ SEC'To'Q 2? WERT Somos -l 1' mos CATALYs-r s TEAM 5*? 1 hEQT Somos 2g M' 55 38 5 QEQYCLE GAS Am/ 54 Edward hfflchoLSogl nvenbor @QRS Clt/Corne United States Patent O CATALY'IIC FLUID vHYDROFORB(IING EMPLOY- ING lNERT HEAT TRANSFER SOLIDS Edward W. S. Nicholson, Baton Rouge, La., assg'nor to Esso Research and Engineering Company, a corporation of Delaware Application April 4, 1951, Serial No. 219,217 4 Claims. (Cl. 196-e-50) This invention pertains to the catalytic conversion of hydrocarbon fractions and particularly to the conversion of hydrocarbonV fractions boiling within the motor fuel boiling range of low knock rating i'nto high octane number motor fuels. Specically this invention pertains to an improved process for upgrading hydrocarbon fractions boiling within the motor fuel or naphtha range by hydroforming or aromatizing the same in a uidized solids reactor system.

Hydroforming is a well known and widely used process for treat-ing hydrocarbon fractions boiling within the motor fuel or na'phtha fange to upgrade the same or increase the a'rinaticity and improve the anti-knock characteristics of said fractions.V By hydroforming is ordinarily meant an operation conducted at elevated teinperaturs' and pressti'res in the presence of solid catalyst particles 'and hydrogen whereby the hydrocarbon fraction is increased iii aromaticity and in which operatron there rs no het consumption or hydrogen. Hydrofoiriiing operations are usually carried out the presence of hydrogen at temperatures or 71504150" F, in the pressure range of about 'SO-3G60 lbs. per sq. inch `and in coh'tac't with such catalysts as molybdenum oxide or chromium oxide, or, ihgeneral, oxides and sourdes of metals or groups 1V, V, V1, VH, and V111 ofthe periodic y'stl f lfflt's, l'n, Ol gerlc''ally supported 'On a bas i Spacing agent Such aS alumina gel, pfcipiatd alumina or zinc illuminate sprhel. Aromatizatioh is oar- Ari'ed out in the presence or absence of hydrogen in 'the PTSC f 'the SBIB gll'l ClaSS f 'alySfS ali lemperatures of about `7504150 Vout at pressures of from atmospheric to at mo's't about l0() lb's. per sq. inch. F

1t has been propo-sea rh application serial No. 188,236 filed October 3, 1950, 110W U. S. Patent N0. 2,689,823, 't0 effect the hydifrmng Of haphh fractions in a flidized solids reactor system in which naphtha vapors are passed continuously through a dense, Yuidized bed of hydrofor'ming catalyst particles in a reaction Zone, spent vcatalyst being continuously "withdrawn from the dense bed and passed toa separate regeneration Zone where inactivating carbonaceous deposits are removed whereupon the regenerated catalyst 'particles are returned to the main reactor vessel. 7In the process disclosed in said application operation has been limited to low catalyst to oil ratios (around 1:1) by selectivity considerations since higher ratios resulted in excessive carbon formation. Moreover, high regeneration temperatures have notbeen possible due to steam deactivation of the catalyst. These factors limit the transfer of heat yfrom the regenerator to the reactor via 'the catalyst and make it necessary to provide cooling coils in the regenerator and `to Vprovide furnaces or other means for supplying heat to the 'reactor either directly or indirectly through preheating the reactants and/ or the hydrogen-rich recycle gas.

It i's Athe object of this invention to provide a process whereby hydrocarbon fractions boiling within the motor fuel range may be hydroforr'ned or aromatiz'ed in an advantageous manner by the uidized 'solids technique.

It is a further object of this invention to provide a process whereby hydrocarbon fractions boiling within the motor fuel range may be hydroformed or aromatized in a iluidized solids reactor system in which all the heat released in the regeneration of the catalyst particles may be readily transferred from the regeneration vessel to the reaction vessel.

it is also an object of this invention to provide a process whereby hydrocarbon fractions boiling within the motor fuel range may be hydroforrned or aromatized by the fluidized solids technique with low catalyst to oil ratios but at high temperatures and without excessive preheating of the naphtha feed and without the circulation of excessive amounts of recycle gas and without heating the recycle gas to excessively high temperatures.

It is a further object of this invention to devise a simple and economical method for transferring the heat of regeneration to the reactor vessel and simultaneously protecting the catalyst from excessively high or inactivating temperatures.

These and other objects will appear more clear from the detailed specification and claims which follow:

It has now been found that the hydroforming or aromatization of petroleum fractions boiling within the 'motor fuel boiling range in a fluidized solids reactor system can be carried out to greater advantage if extraneous heat-carrying or heat transfer solids are circulated between the reactor vessel and the regeneration vessel in a particular manner. It is, of course, old to use so-called pebble heaters to heat up an extraneous heat-carrying solid for circulation through a reaction zone in order to convey some or all of the heat required for carrying out the desired reaction or operation into the reaction zone. in accordance with the present invention a circulating stream of inert fluidized solids is provided to carry the necessary heat from the regenerator to the reactor, thus making it possible to operate with as low a circulation rate of catalyst as desired, thus reducing carbon formation and also oxygen as well as hydrogen requirements. The relative rates of circulation of catalyst and inert heat transfer solids are controlled by separate slide valves on individual standpipes through which the two solids streams are withdrawn from the reactor. The stream of inert solids is discharged from the reactor into the stream of regeneration air for transport to the regenerator upstream of the point of addition of the spent catalyst so that the heat absorptive capacity of the inert solids will preclude overheatingV the catalyst through combustion of the carbonaceous deposits thereon during its travel through the transfer line into the regenerator vessel. Extraneous heat may be added, if desired, to the circulating solids stream by introducing a combustible oil or gas directly into the regenerator. The mixture of inert heat transfer solids with the relatively small amount of catalyst is discharged from the regenerator via a standpipe, or the like into a stream of recycle gas which carries the mixture back to the reactor. Because of the great flexibility possible in the amount of heat provided by the circulating inert solids, it is not necessary to preheat the feed to temperatures Vthat might result in thermal degradation of the feed. In fact, it is possible to eliminate entirely the feed preheat furnace and to heat the feed stream only to the temperatures possible by heat exchange with product streams. Further, it is not necessary to circulate such large volumes of recycle gas and it is not necessary to heat the recycle gas to the high temperatures of about l200 F. that are normally required. This eliminates or minimizes 'the possibility of coking in the recycle gas fired coil. Moreover, it is possible with this arrangement to operate with recycle gas temperatures of lO0O F. or less, which permits using carbon steel furnace tubes in temperature through line 12 to suitable distributor nozzles Y13 in the lower portion of the reactor vessel 10.V Catalyst and inert heat transfer solids are supplied to the reactor vessel 19 in finely ,divided condition in suspension in a hydrogen-containing gas, preferably recycle hydrogen-rich process gas through inlet line 14 which discharges into inlet cone l in the lower portion of the reactor Vessel.

VSolid particles and carrying gas are discharged from the inlet cone through a perforated plate Vor grid 16 which rserves to distribute the incoming material uniformly over the entire cross section of the reactor vessel.

Suitable catalysts includeV group Vl metal oxides such as molybdenum oXide, chromium oxide'or tungsten oxide or mixtures, thereof preferably upon a carrier such as activated alumina,Y zinc aluminate Vspinel or the like. The catalyst particles should, for proper iluidization, be between 200 and 400 mesh in size or about 0-200 microns in diameter'with a major proportion between 2O and 80 microns.

The inert, heat transfer solids are preferably coarser and/ or of greater density than the catalyst used in the process. Typical solids which may be used are metal spheres or ceramic balls or granules such as corundum or gamma aluminafused silica or the like. It is Vnecessary that these materials have no adverse effects upon the catalytic reactions occurring in the reactor and that they be stable or resistant to breakdown due to the temperature and mechanical action to which they are subjected. Unless the inert heat transfer solidsV are relatively heavy orhave a bulk densityv at least 1.5 times die bulk density of the catalyst, they should be no smaller than about 100 microns and should preferably be in the range of 12S-300 microns.

The feed or charging stock vapors introduced via 'nozzles 13 and the hydrogen-containing gas supplied through inlet chamber and distributor grid 16 pass through the reaction zone at a superficial velocity of about 0.2 to 0.9 ft. per second at reactor'conditions depending upon the pressure. For example, the velocity should be below 0.6 ft per/second 'in the pressure range of 2430-250 lbs. per sq. inch gauge. The velocity should be suicient to maintain a dense turbuient, liquid simulating bed 18 of catalyst and inert solid particles and gas having a definite level 19 with a dilute phase suspension of solids and product vapors 26 thereabove.

A-Vvertical conduit 22 is arranged alongside the reactor vessel i@ for receiving catalyst directly from the dense,

'uidized bed 18 through connector pipe 23. An inlet 24 for the introduction of steam or other stripping gas is provided in the iower part of ,conduit 22 in order to displace, strip otf or desorb hydrogen and/or hydrocarbons accompanying the catalyst particles withdrawn from the dense bed 18. The line 25 connecting the top of conduit 22 vwith the upper part of reactor'lt) serves Vto conduct stripping gas and stripped vapors into the dilute phase in the reactor for admixture with product vapors. While the conduit or stripper 22 is shown arranged externally ofthe reactor vessel, it willbe understood that it could also be arranged within the vessel itself in which event the conduit would be open at the top and extend into the dilute phase 20 and one or more restriction orifices would be providedfin the wall of the conduit below the dense bed intoV the conduit 22.

Vis supplied under pressure and preheated to a desired f current ow of catalyst and oil vapors up through the Y bed 18 and to obtain a minimum of short-circuiting or passage of catalyst into connector `23 and conduit 22 immediately after it entersthe dense bed 18. The connector 23 should be suiciently below the maximum bed level 19 to take care o f any normal fluctuations in the depth ofthe dense bed.KV More than one connector 23 may be provided at different levels and each connector may be provided with means to control the flow of catalyst into conduit 22. The lower end of conduit 22 is necked down and connects to conduit 27 to formitherewith a standpipe for developing a uistatic pressure suicient to cause the catalyst to ow through a control or slide valve 28 into transfer line 30 and thence into the regenerator 40, p

The vaporous reaction products discharged overhead from the dense bed as well as the stripping gases discharged from the conduit 22rpass through a cyclone separator 31 or'the likeY which serves to remove small amounts of catalyst that are entrained in the gaseous products. VThe separated catalyst particles are returned to the dense bed by the dip pipe shown and the vaporous products substantially free of catalyst are taken overhead through outlet line 32 and passed to suitable recovery orv processing equipment.

The inert, heat transfer solid particles are withdrawn from the bottom of the reactor vessel through a passageway surrounding the inlet chamberV 15 and pass in admisture with finely divided catalyst particles through line 33 into chamber V34. Suitable non-fluidizable packing such as Raschg rings, Berl saddles or the like isarranged in the lower part of chamber 34 and an inlet 35 is provided at the base of the chamber for introducing steam or other inert gas for elutriating or effecting separation of finely divided catalyst particles from the inert, heat The inert heat transfer solid particles admixed with a` small amount of catalyst particles are discharged from the bottom of chamber 34 into conduit 37 which serves as a standpipe for building up a lluistatic pressure inthe heat transfer particles sufficient to cause them to flow through a slide valve or control valve 38 intoconduit 30 Y where they are picked up by a stream of regeneration air and conveyed into the regenerator 40.

The point of introduction of the inert heat transfer solids into the transfer line 30 is upstream from the point of introduction of the main streamv of spent catalyst particles. In this way substantial amounts lof inert heat transfer solids are intimately mixed with the spent catalyst particles as soon as they come into contact with the regeneration air. Since the rate of burning of hydrogen adsorbed upon the catalyst as well as of the carbonaceous deposits in contact with the particular catalyst components used in extremely high, the inert heat transfer solid particles serve to absorb much of the heat of regeneration and thereby prevent overheating of the catalyst as would invariably occur in the spent catalyst was passed alone efr-omer with the regeneration a'i through the transfer line into theiregener'ato'r. g

The mixture of catalyst, inert-heat 'tfaisfer'solis and regeneration gas is discharged from transfer line 30 into inlet chamber 4l at the bottom of regehera'tr 40. A perforated distributor plate or grid 42 covers the top of the inlet chamber and serves to distribute the incominixture uniformly over the entire cross Vsection of the regener'ator. The velocity of the gases passing lthrough regenerator 40Vis so controlled that a dense, highly turbulent fluidi'zed b'ed of catalyst 'and inert heat 'transfer solids 43 having a denite -level 44 is iformed in the regene'r'tor. The superficial velocity fof 'the Vregerier'atio'n gas through the regenerat'or'may fange 'from 0:3 to l-.S

feet per second depending upon the pressure. For ex- Y ample at regeneration pressures of about 2'00-300 lbs. per sq. inch the superficial velocity shoiild be about 1.0 ft. per second or lower.

In v'the event that the relomnng operation in reactor does not form 'sucient carbon to maintain vheat balance in the system, torch oil l"or 'gas may be supplied to a nozzle 45 to heat the mixture of catalyst and heat transfer solids Vto the desired temperature.

The weight ratio Vof inert solids to catalyst circulated Afrom the reactor 18 to the regeneratonli may vary from about l to about 100 depending upon the relative amount of heat provided by thenaphtha and recycle gas streams Vas compared tothat supplied by the irculatin g inert solids. Temperature of regeneration may be between 1000 and 1200 F., and reactor temperatures may be in the range of 800 to l000 F. Catalyst-to-oil ratios, which in this system are independent of heat balance considerations, may be varied from about 0.1 to 5 pounds of catalyst per pound of oil, with values of 0.3 to l being in the more desirable range. Temperature of the preheated recycle gas may be in the range of 800 to 1200 F., with temperatures below 1000 F. being preferable in order to obviate the use of alloy tubes in the furnace. Recycle gas rates of 1000 to 10,000 cu. ft./ bbl. may be employed, but rates of 1000 to 3000 cu. ft./bbl. are generally preferable. The naphtha feed may be preheated to from 500 to 1000 F., with the optimum range being 600 to 900 F. It is possible with this system to limit naphtha preheat to 600 F., obtainable by heat exchange with product streams, and thus eliminate the necessity for a naphtha preheat furnace.

Combustion gases pass overhead from the dense uidized bed 43 and pass through one or more cyclone separators 46 or the like arranged at the top of the regenerator vessel to remove the bulk-of the entrained solid particles which are returned to the dense bed by the dip pipe 47 and are then discharged via line 48 to the atmosphere or to heat or energy recovery equipment. A well 49 extends above grid 42 into the lower portion of the dense bed 43. A mixture of inert heat transfer solids and catalyst passes from the dense bed 43 into the well 49 and thence through conduit 50 countercurrent to a stream of steam or other inert stripping gas which strips out combustion or regeneration gases that are entrained with the mixture leaving dense bed 43. The stripped mixture of solids pass into standpipe 52 wherein a sufhcient uistatic pressure is developed to overcome the pressure drop taken by the solids passing through the slide or control valve S3, transfer line 14 into reactor 10. The mixture of inert solids and catalyst discharged from standpipe 52 is picked up' by a stream of hydrogen-containing recycle gas supplied through line 54. The length of the transfer line and the size of the inlet chamber should be so designed as to assure adequate Contact time between the catalyst and the hydrogen-containing gas to effect reduction thereof or reconversion to its more active form. Ordinarily contact times of about l to 5 seconds should suice to recondition the catalyst.

Following are examples of applications of the system to the hydroforming of a 200 to 350 F. virgin naphtha having @Clear octane moitier by the Research method of 45 to 50 to yield a finished gasoline of `95 to 100 Rc'- s'ear'ch 'clear octane number.

Opations 'are all on a catalyst consisting f about -9 per cent molybdenum oxide' impregnated on activated alumina or alumina gel, and at a pressure of about 200 -p. s. 1. g.

Column .A B C D Reactor Temperature, F 900 900 900 950 Catalyst/oil weight ratio l 0.5 o. 5 0.5 Recycle Gas Rate, cu.-t ./bbl 3,000 1, 500 1, 500 l, 500 Regenerator Temperature, F 1,150 1, 150 1, 150 1, 100 Naphthaieed'temperature, F 950 '800 600 800 Recycle Gas Temperature, F 1,185 1,000 900 1,000 Approx. inert 'solids/oil wt. ratio 0 5 9 9 Column A in the above tabulation lists 'conditions i'mposed in the conventional system by heat balance considerations when no inert heat transfer solids are employed. Column B illustrates that, by circulating inert lieat transfer solids 'sucha's sand or inactive silica gel at 'a rate'f approximately 5 pounds of solids per'pound of npht'ha feed, the catalyst-'to-oil ratio and 'the 'recycle gas rate may be lowered to values more desirable from product distribu- 'tion considerations, ajiid vthe optima feed 'and recycle gas temperatures may 'be app'rciably lowered so that the possibility vof furnace cbkihg is eliminated and alloy Vtubes inthe recycle gas furnace are not needed. 'A's shw'n by colu'riin C, increasingv'the inert solids-'to-oil weight ratio to about 9 permits vfurther lowering of the recycle gas temperature, and permits lowering naphtha feed preheat temperature to a level which can be attained by heat exchange only and eliminates the necessity for a feed furnace. Column D illustrates the fact that a reactor temperature of 950 F. can easily be achieved even at reduced regenerator temperature by employing an inert solids-tooil ratio of approximately 9. In those cases employing inert heat transfer solids such as sand or inactive gels, the catalyst preferably consists of particles in the range of 0-80 microns, and the inert solids are ground to provide a particle size range of about -200 microns. It is not essential that a complete separation of catalyst from inert solids be obtained in the elutriating section 34 because any catalyst enuained with the inert solids from this zone can be compensated for by reducing the rate at which catalyst is withdrawn from the reactor 18 through standpipe 27 and control valve 28.

The foregoing description contains a limited number of embodiments of the present invention. lt will be understood that numerous variations are possible without departing from the scope of the following claims.

What is claimed is:

1. In the method of reforming hydrocarbon fractions boiling within the naphtha range in contact with a mixture of finely divided reforming catalysts and inert heat transfer solids in a dense iiuidized bed the improvement which comprises withdrawing a stream of inert heat transfer solids and a stream of finely divided spent catalyst particles from the reaction zone, adding the inert heat transfer solids to a stream of regeneration gas, discharging the stream of spent catalyst particles into mixture of inert solids and regeneration gas, discharging the resultant mixture into a regeneration zone, withdrawing a mixture of inert solids and regenerated catalyst particles from the regeneration zone and recycling the same to the reaction zone.

2. In the method of reforming hydrocarbon fractions boiling within the naphtha range in contact with a mixture of finely divided reforming catalyst and inert heat transfer solids in a dense, uidized bed in a reaction zone the improvement which comprises withdrawing a stream of nely divided spent catalyst particles from the upper part of the dense uidized bed, withdrawing a mixture of inert heat transfer solids and finely divided catalyst particles from the bottom of the dense, iluidized bed, passing the of inert solids and regenerated catalyst particles from the `regeneration zone and recycling the same to the reaction zone.

' '3. In the method of reforming hydrocarbon fractions boiling Within the naphthaV range in contact with a mixture Yof finely divided `reforming catalyst and inert heat transfer solids in Va dense fluidized bed the improvement which comprises withdrawing a stream of inert heat transfer solids and a stream of nely divided spent catalyst particles from the reaction zone, adding the inert heat transfer solids to a stream of regeneration gas, discharging the stream of spent catalyst particles into mixture of inert solids and regeneration gas, discharging the resultant Vmixture into a regeneration zone, burning an extraneousfuel in the regeneration zone in order to heat the mixture of inert solids and catalyst, withdrawing 'a mixture of inert solids and regenerated catalyst particles from the regeneration zone and recycling the same to the reaction zone.

4. VIn the method of reforming hydrocarbon fractions boiling within the naphtha range in contact with a mix- 8 ture of nely divided reforming catalyst and inert heat transfer solids in a dense, lluidized bed in a reaction'zone the improvement which comprises withdrawing a stream of finely divided spent catalystparticles from the upper part of the dense uidized bed, withdrawing a mixture of inert vheat transfer solids and finelyV divided catalyst particles from the bottom of the dense uidized bed, passing the latter mixture through an elutriation zone, separating a substantial part of theV catalyst particles from said mixture andrreturning the separated catalyst particlesto the Vreaction zone,' withdrawing a stream of inert heat transfer solids from the elutriation zone, adding the inert heat transfer solidsrto a stream of'regeneration gas,y discharging the stream of spent catalyst particles intol mixture of inert solids and regeneration gas,

discharging therresultant mixture into a regenerationV zone, burning anrextraneous fuel in the regeneration zone in order to heat the mixture of Yinert solids and catalyst, withdrawing a mixture of inert *solids and regenerated catalyst particles frompthe regeneration zone and recycling vthe same to the reaction zone.

` References Cited in the file of this patent UNITED STATES PATENTS Holt et al. July 27, 1943 2,393,636 Johnson' Ian. 29, 1946 2,446,247 Scheineman- Aug. 3, 1948 2,472,844

Munday et al. June 14, 1949 

1. IN THE METHOD OF REFORMING HYDROCARBON FRACTIONS BOILING WITHIN THE NAPHTHA RANGE IN CONTACT WITH A MIXTURE OF FINELY DIVIDED REFORMING CATALYSTS AND INERT HEAT TRANSFER SOLIDS IN A DENSE FLUIDIZED BED THE IMPROVEMENT WHICH COMPRISES WITHDRAWING A STREAM OF INERT HEAT TRANSFER SOLIDS AND A STREAM OF FINELY DIVIDED SPENT CATALYST PARTICLES FROM THE REACTION ZONE, ADDING THE INERT HEAT TRANSFER SOLIDS TO A STREAM OF REGENERATION GAS, DISCHARGING THE STREAM OF SPENT CATALYST PARTICLES INTO MIXTURE OF INERT SOLIDS AND REGENERATION GAS, DISCHARGING THE RESULTANT MIXTURE INTO A REGENERATION ZONE, WITHDRAWING A MIXTURE OF INERT SOLIDS AND REGENERATED CATALYST PARTICLES FROM THE REGENERATION ZONE AND RECYCLING THE SAME TO THE REACTION ZONE. 